Optical compensation sheet and liquid crystal display device

ABSTRACT

An optical compensation sheet, which contains a cellulose acylate film that contains 1 to 20 parts by mass of a retardation controlling agent, to 100 parts by mass of a cellulose acylate, wherein the retardation controlling agent comprises at least two compounds different in Re/Rth ratios each other; and a liquid crystal display device, which contains the optical compensation sheet.

This application is a 371 of PCT/JP2006/303818 filed Feb. 22, 2006

TECHNICAL FIELD

The present invention relates to an optical compensation sheet and aliquid crystal display device; and particularly to an opticalcompensation sheet made of only one cellulose acylate film, and apolarizing plate and a liquid crystal display device using the opticalcompensation sheet.

BACKGROUND ART

Among cellulose films, a cellulose acetate film has higher opticalisotropy (a lower retardation value) than other polymer films.Therefore, it is common to use a cellulose acetate film in applicationsrequiring optical isotropy, e.g. for a polarizing plate. On the otherhand, it is demanded that optical compensation sheets (retardation films(or phase-contrast films or phase difference films)) for use, forexample, in a liquid crystal display device, have optical anisotropy(high retardation value), on the contrary. Therefore, a syntheticpolymer film, e.g. a polycarbonate film or polysulfone film, which has ahigh retardation value, is commonly used as the optical compensationsheet.

As described above, in the technical fields of optical materials, asynthetic polymer film is used when it is required for a polymer film tohave optical anisotropy (high retardation value), and a celluloseacetate film is used when it is required for a polymer film to haveoptical isotropy (low retardation value), in general.

However, in these days, another-type of cellulose acetate film having ahigh retardation value is demanded, so that it can also be used inapplications for which optical anisotropy is required, and technologiesto meet this are proposed (for example, European Patent ApplicationPublication (Laid-Open) No. EP0911656A2). In the above EP0911656A2, anaromatic compound having at least two aromatic rings, and particularly acompound having a 1,3,5-triazine ring, is added, and stretching iscarried out, in order for a cellulose triacetate film to have a highretardation value, in practice.

Generally, it is known that a cellulose triacetate is a high-molecularraw material that can be stretched (or orientated) with difficulty, andit is difficult to make the cellulose triacetate have a largebirefringence. However, in the above EP0911656A2, additives areorientated at the same time by stretching, thereby making it possible toincrease birefringence and attaining a high retardation value. This filmhas such a merit that an inexpensive and thin-film liquid crystaldisplay device can be obtained, because this film can double as aprotective film of a polarizing plate.

In recent years, making thinner films for liquid crystal cells has beenessential to creating lighter-weight liquid crystal displays, reducingmanufacturing cost of liquid crystal displays, or increasing responsespeed of liquid crystal displays. The optical performance required foran optical compensation sheet is, therefore, a higher Re retardationvalue, and it has become necessary to provide a film having a lower Rthretardation value.

However, the present inventors, having made earnest studies as to themethod disclosed in EP0911656A2, have, as a result, clarified that thismethod has the problem that it is difficult to set the Re retardationvalue and Rth retardation value individually, they cannot be setcompatibly by the aforementioned method. There are, besides the aboveEP0911656A2, patent documents, for example JP-A-2001-116926 (“JP-A”means unexamined published Japanese patent application), which disclosetechniques concerning the optical performance of a phase-contrast film.In the publications, no method of making a desired Re value and adesired Rth value compatible with each other is clearly described.

In the case of considering that the thickness of a film is fixed, theretardation of the film is determined by the refractive index and amountof a raw material and the orientation state. In the method disclosed inthe above EP0911656A2, the retardation of the film is determined by thethree-axis refractive indexes and orientation state of the cellulosetriacetate, as well as the refractive index, amount to be added, andorientation state of the disk-like compound serving as an additive.

The Re retardation value and the Rth retardation value are both definedas refractive indexes in three-axis directions, and therefore the ratioRe/Rth is mostly determined by an additive that largely contributes tothe development of retardation. By investigating the Re/Rth ratio vs.the stretch ratio (or orientation ratio), it was found that both areproportional to each other, and the Re/Rth ratio is increased as thestretch ratio is increased. In the case of varying the amount to beadded, the same proportional relation is also obtained: The Re/Rth ratiois increased as the amount to be added is increased. The gradient of theRe/Rth ratio to the stretch ratio is determined by the raw material tobe added. It was found that, in the case of the disk-like compounddescribed specifically in the above EP0911656A2, the gradient is small.

The orientation states of cellulose triacetate and additives, whichorientation determines the retardation value, differ depending on thestretching method. Generally, a roll stretching method and a tenterstretching method are known, as examples of a monoaxially stretchingmethod. In the former method, the width of a film is shrunk, so that Retends to be developed. In the latter method, a film is stretched in thetransverse direction under the condition that the conveying direction islimited, and Re is scarcely made large. As a result, the Re/Rth ratio tothe stretch ratio is smaller in the latter case than in the former case.Because the tenter stretching method has a tendency to decrease thedispersions of film thickness and optical performances within a givenplane, it is suitable as a method of producing an optical compensationsheet for a liquid crystal display device. When this method is appliedto the aforementioned disclosed example, the increment of the Re/Rthratio is about 0.01 or less, per 1% of the stretch ratio. When thetarget value of Re is close to the target value of Rth and the Re/Rthratio is about 0.5, the stretch ratio must be 50% or more. It isdifficult to actually attain this stretch ratio stably in the case ofcellulose triacetate film resistant to stretching.

Also, as to the amount to be added, it is difficult to attain theoptical performances to be intended by a possible increase in the amountto be added.

Other and further features and advantages of the invention will appearmore fully from the following description.

DISCLOSURE OF INVENTION

The present inventors have found that, to enlarge the controllableregion of the Re/Rth vs. the stretch ratio in the case of attainingoptimum Re and Rth values by a tenter stretching method as describedabove, the controllable region of the Re/Rth vs. the stretch ratio canbe enlarged, by using a disk-like compound, as described in the aboveEP0911656A2, and a compound represented by the following formula (II),together as additives. The inventors have also found that an opticalcompensation sheet having an optical performance that cannot be attainedby conventional methods, can be obtained. The present invention was thusattained based on these findings.

According to the present invention, there is provided the followingmeans:

(1) An optical compensation sheet, comprising a cellulose acylate filmthat contains 1 to 20 parts by mass of a retardation controlling agent,to 100 parts by mass of a cellulose acylate, wherein the retardationcontrolling agent comprises at least two compounds different in Re/Rthratios each other.

(2) The optical compensation sheet according to Item (1), wherein theoptical compensation sheet comprises a cellulose acylate film stretchedat a stretch ratio of 3 to 100%.

(3) The optical compensation sheet according to Item (1) or (2), whereinthe content of the two compounds contained in the retardationcontrolling agent is 1 to 20 parts by mass in sum, to 100 parts by massof the cellulose acylate.

(4) The optical compensation sheet according to any one of Items (1) to(3), wherein one of the two compounds contained in the retardationcontrolling agent exhibits a Re/Rth ratio of less than 0.35, and theother exhibits a Re/Rth ratio of not less than 0.35.

(5) The optical compensation sheet according to Item (4), wherein thecompound exhibiting a Re/Rth ratio of less than 0.35 is represented byformula (I):

wherein X¹ represents a single bond, —NR⁴—, —O—, or —S—; X² represents asingle bond, —NR⁵—, —O—, or —S—; X³ represents a single bond, —NR⁶—,—O—, or —S—; R¹, R² and R³ each independently represent an alkyl group,an alkenyl group, an aryl group, or a heterocyclic group; and R⁴, R⁵ andR⁶ each independently represent a hydrogen atom, an alkyl group, analkenyl group, an aryl group, or a heterocyclic group.

(6) The optical compensation sheet according to Item (4), wherein thecompound exhibiting a Re/Rth ratio of less than 0.35 is represented byformula (II):Ar¹-L¹

Ar²-L²

_(n)Ar³  Formula (II)

wherein Ar¹, Ar², and Ar³ each independently represent an aryl group oran aromatic heterocyclic group; L¹ and L² each independently represent asingle bond or a divalent linking group; n represents an integer of 3 ormore; and a plurality of the Ar² moieties may be the same or different,and a plurality of the L² moieties may be the same or different.

(7) The optical compensation sheet according to Item (4), wherein thecompound exhibiting a Re/Rth ratio of not less than 0.35 is representedby formula (III):Ar¹¹-L¹²-X-L¹³-Ar¹²  Formula (III)

wherein Ar¹¹ and Ar¹² each independently represent an aromatic group;L¹² and L¹³ each independently represent a divalent linking groupselected from the group consisting of an alkylene group, —O—, —CO—, anda combination thereof; and X represents 1,4-cyclohexylene, vinylene, orethynylene.

(8) The optical compensation sheet according to any of Items (1) to (7),wherein the retardation controlling agent is a compound represented byformula (IV):

wherein R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ each independently represent ahydrogen atom or a substituent.

(9) The optical compensation sheet according to any one of Items (1) to(8), wherein the cellulose acetate film has a surface energy of 55 mN/mto 75 mN/m.

(10) A method of producing an optical compensation sheet according toany one of Items (1) to (9), comprising the steps of:

feeding a cellulose acylate film in the longitudinal direction of thefilm; and

stretching the cellulose acylate film in a direction perpendicular tothe longitudinal direction,

wherein the cellulose acylate film has a residual solvent content of 2%by mass to 50% by mass when the stretching is started, and the film hasa slow axis in a direction perpendicular to the longitudinal directionof the film.

(11) The optical compensation sheet according to any one of Items (1) to(9) or the method of producing an optical compensation sheet accordingto Item (10), wherein the cellulose acylate is a cellulose acetatehaving an acetylation degree of 59.0% to 61.5%.

(12) The optical compensation sheet according to any one of Items (1) to(11) or the method of producing an optical compensation sheet accordingto Item (10) or (11), wherein the cellulose acylate film is comprised ofa cellulose acylate in which a hydroxyl group of the cellulose ispartially substituted with an acetyl group or with an acyl group having3 to 22 carbon atoms, and wherein a substitution degree A of the acetylgroup in the cellulose acylate and a substitution degree B of the acylgroup having 3 to 22 carbon atoms in the cellulose acylate satisfyexpression (III).2≦A+B≦3.0  Expression (III)

(13) The optical compensation sheet or the method of producing anoptical compensation sheet according to Item (12), wherein the acylgroup having 3 to 22 carbon atoms in the cellulose acylate is a butanoylgroup or a propionyl group.

(14) A liquid crystal display device, comprising a liquid crystal cell,and two polarizing plates disposed on both sides of the liquid crystalcell, said polarizing plate comprising a polarizing film and twotransparent protective films disposed on both sides of the polarizingfilm, wherein the optical compensation sheet according to any one ofItems (1) to (13) is disposed between the liquid crystal cell and atleast one polarizing film, and wherein a slow axis of the celluloseacylate film and a transmission axis of the polarizing film adjacent tothe cellulose acylate film are arranged in substantially parallel toeach other.

(15) The liquid crystal display device according to Item (14), whereinthe liquid crystal display device has a VA mode.

Herein, the Re and the Rth indicate the in-plane retardation and theretardation in the direction of the thickness, respectively. The Re ismeasured by making light having a wavelength of 590 nm incident in thedirection of the normal of the film in KOBRA 21ADH (trade name,manufactured by Oji Scientific Instruments). The Rth is a valuecalculated by KOBRA 21ADH based on (i) the retardation values measuredin total three directions, these retardation values including the aboveRe, the retardation value measured by allowing light having a wavelengthof λnm to be incident from a direction inclined at an angle of +40° withthe direction of the normal of the film by adopting the slow axis (whichis determined by the KOBRA 21ADH) within the surface as a slant axis(rotation axis), and the retardation value measured by allowing lighthaving a wavelength of λnm to be incident from a direction inclined atan angle of −40° with the direction of the normal of the film byadopting the slow axis within the surface as a slant axis (rotationaxis); (ii) an hypothetical value of the average refractive index; and(iii) a film thickness input. Herein, as the hypothetical value of theaverage refractive index, use may be made, for example, of valuesdescribed in “Polymer Handbook” (JOHN WILEY & SONS, INC.) and valuesdescribed in catalogues of various optical films. Unknown averagerefractive indexes may be determined by Abbe refractometer. Averagerefractive indexes of major optical films are exemplified in below:cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate(1.59), polymethyl methacrylate (1.49), and polystyrene (1.59). KOBRA21ADH calculates nx, ny and nz, by inputting these hypothetical valuesof the average refractive index and the film thickness. The calculatednx, ny and nz are utilized to further calculate Nz=(nx−nz)/(nx−ny).

In the present invention, the term “compounds different in Re/Rth ratioseach other” means compounds exhibiting values of Re/Rth ratios differentin each other, in which said ratio is calculated from the measured Reand Rth values of a triacetyl cellulose that contains any one of thecompounds and that is produced through dope preparation, casting, andstretching.

Herein, specifically, the value of Re/Rth ratio is calculated from Reand Rth measured with light of wavelength 590 nm in KOBRA 21ADH (tradename, manufactured by Oji Scientific Instruments), with respect to afilm produced by a process of the steps of: casting a dope prepared asdescribed below on a glass plate, drying the dope at 70° C. for 6minutes, separating the dried dope from the glass plate, and thenfurther drying it at 100° C. for 10 minutes and at 120° C. for 20minutes, and stretching the dried product by 20% with a fixed-endstretching machine, to form the film thus cast and dried. Since thesevalues vary with the content of the compound and the stretch ratio, thevalue obtained with respect to a film produced with an addition amountof 2% by mass and stretched by 20% is used as a control value.

Triacetyl cellulose (acetylation degree: 60.9%) 100 mass parts Triphenylphosphate (plasticizer) 7.8 mass parts Biphenyldiphenyl phosphate(plasticizer) 3.9 mass parts Methylene chloride 318 mass parts Methanol47 mass parts Compound (retardation controlling agent) 2 mass parts

By the use of the optical compensation sheet of the present invention,liquid crystal cells can be optically compensated with the opticalcompensation sheet consisting only of one cellulose acylate film.According to the present invention, it is also possible to obtainoptical compensation sheets having a combination of Re and Rth in a verywide range, which would otherwise not be reached by conventionaltechniques.

When the optical compensation sheet of the present invention is used asone of the protective films of the polarizing plate, it is possible toadd an optical compensation function to the polarizing plate, withoutincreasing the number of structural elements of the polarizing plate.

The aforementioned optical compensation sheet composed only of thecellulose acetate film, and the polarizing plate that uses the opticalcompensation sheet as a protective film, each can be advantageously usedparticularly in VA mode or OCB mode liquid crystal display devices.

BEST MODE FOR CARRYING OUT INVENTION

In the present invention, it is preferable that the Re retardation valueof the cellulose acylate film be adjusted to 60 to 120 nm and the Rthretardation value be adjusted to 100 to 250 nm.

In the present invention, it is possible to control a variation ofRe/Rth per 1% of the stretch ratio to 0.01 to 0.1. Herein, the variationin Re/Rth per 1% of the stretch ratio may be found from the gradient ofthe line obtained when each Re/Rth ratio vs. at least three stretchratios of each 5% or more is primarily approximated.

The birefringence index (nx−ny) of the cellulose acylate film ispreferably in the range of 0.0002 to 0.0009, more preferably in therange of 0.00025 to 0.0009, and most preferably in the range of 0.00035to 0.0009.

The birefringence index {(nx+ny)/2−nz} of the cellulose acylate film inthe thickness direction is preferably in the range of 0.0006 to 0.005,more preferably in the range of 0.0008 to 0.005, and most preferably inthe range of 0.0012 to 0.005.

(Cellulose Acylate Film)

Any known cotton material may be used for the cellulose acylate for usein the present invention (for example, see Journal of TechnicalDisclosure No. 2001-1745, published by Japan Institute of Invention andInnovation). The cellulose acylate may also be synthesized by any knownmethod (for example, see Uda et al., “Mokuzai Kagaku (Wood Chemistry)”,published by KYORITSU SHUPPAN CO., LTD., 1968, pp. 180-190). The averagepolymerization degree in terms of viscosity of a cellulose acylate thatcan be used in the present invention is preferably from 200 to 700, morepreferably from 250 to 500, and particularly preferably from 250 to 350.The cellulose ester for use in the present invention preferably has anarrow molecular mass distribution in terms of Mw/Mn (Mw is a massaverage molecular mass and Mn is a number average molecular mass) asmeasured by gel permeation chromatography. Specifically, the value ofMw/Mn is preferably from 1.5 to 5.0, more preferably from 2.0 to 4.5,and most preferably from 2.0 to 4.0.

As the acyl group of the cellulose acylate film, there is no particularlimitation to the acyl group, and an acetyl group, propionyl group orbutyryl group is preferably used, and an acetyl group is particularlypreferably used. The degree of substitution of all acyl groups ispreferably 1.5 to 3.0, more preferably 2.7 to 3.0 and particularlypreferably 2.8 to 2.95. Herein, the degree of substitution of an acylgroup(s) is a value calculated according to ASTM D817.

It is most preferable that the acyl group be an acetyl group. When acellulose acetate containing an acetyl group as the acyl group is used,the degree of acetylation is preferably 59.0 to 62.5%, more preferably59.0 to 61.5%. When the degree of acetylation is within this range, theRe is not larger than a desired value by a conveyance tension at thetime of casting, the in-plane dispersion of Re is decreased, and avariation in retardation value due to change in temperature and humidityis not increased.

The degree of substitution of an acyl group at the sixth position ispreferably 0.9 or more, from the viewpoint of suppressing thedispersions of Re and Rth.

(Retardation Controlling Agent)

In the present invention, the cellulose acylate film contains at leasttwo compounds that have different properties with respect to developmentof optical anisotropy (Re/Rth ratio) upon stretching. With respect tothe two compounds to be used exhibiting different Re/Rth ratios, thedifference between the Re/Rth ratios is preferably 0.05 or more, morepreferably 0.10 or more. Preferably, at least two compounds are utilizedin combination, one compound of which exhibits a Re/Rth ratio of lessthan 0.35 when a cellulose triacetate film containing said compound isstretched, and another of which exhibits a Re/Rth ratio of not less than0.35 when a cellulose triacetate film containing said compound isstretched.

Preferable examples of the compound exhibiting a Re/Rth ratio of lessthan 0.35, include those represented by formula (I) or (II).

The compound represented by formula (I) is described below.

In formula (I), X¹ represents a single bond, —NR⁴—, —O—, or —S—; X²represents a single bond, —NR⁵—, —O—, or —S—; X³ represents a singlebond, —NR⁶—, —O—, or —S—; R¹, R² and R³ each independently represent analkyl group, an alkenyl group, an aryl group, or a heterocyclic group;and R⁴, R⁵ and R⁶ each independently represent a hydrogen atom, an alkylgroup, an alkenyl group, an aryl group, or a heterocyclic group.

The compound represented by formula (I) has a 1,3,5-triazine ring, andmay be preferably an aromatic compound having at least two aromaticrings.

In particular, the compound represented by formula (I) is preferably amelamine compound. In the melamine compound represented by formula (I),X¹, X² and X³ are —NR⁴—, —NR⁵— and —NR⁶—, respectively, or alternativelyX¹, X² and X³ are each a single bond, and R¹, R² and R³ are each aheterocyclic group having a free atomic valence on a nitrogen atom. Thegroups —X¹—R¹, —X²—R² and —X³—R³ are preferably the same. In particular,R¹, R² and R³ each preferably are an aryl group. In particular, R⁴, R⁵and R⁶ each preferably are a hydrogen atom.

For the alkyl group, a chain alkyl group is preferable to a cyclic alkylgroup, and a linear chain alkyl group is preferable to a branched chainalkyl group.

The number of carbon atoms in the alkyl group is preferably from 1 to30, more preferably from 1 to 20, still more preferably from 1 to 10,even more preferably from 1 to 8, most preferably from 1 to 6. The alkylgroup may have a substituent or substituents. Examples of thesubstituent include a halogen atom, an alkoxy group (e.g. methoxy,ethoxy and epoxyethyloxy), and an acyloxy group (e.g. acryloyloxy andmethacryloyloxy). For the alkenyl group, a chain alkenyl group ispreferable to a cyclic alkenyl group, and a linear chain alkenyl groupis preferable to a branched chain alkenyl group. The number of carbonatoms in the alkenyl group is preferably from 2 to 30, more preferablyfrom 2 to 20, still more preferably from 2 to 10, even more preferablyfrom 2 to 8, most preferably from 2 to 6. The alkenyl group may have asubstituent or substituents. Examples of the substituent include ahalogen atom, an alkoxy group (e.g. methoxy, ethoxy and epoxyethyloxy),and an acyloxy group (e.g. acryloyloxy and methacryloyloxy).

The aryl group is preferably phenyl or naphthyl, particularly preferablyphenyl. The aryl group may have a substituent or substituents. Examplesof the substituent include a halogen atom, hydroxyl, cyano, nitro,carboxyl, and groups of alkyl, alkenyl, aryl, alkoxy, alkenyloxy,aryloxy, acyloxy, alkoxycarbonyl, alkenyloxycarbonyl, aryloxycarbonyl,sulfamoyl, alkyl-substituted sulfamoyl, alkenyl-substituted sulfamoyl,aryl-substituted sulfamoyl, sulfonamido, carbamoyl, alkyl-substitutedcarbamoyl, alkenyl-substituted carbamoyl, aryl-substituted carbamoyl,amido, alkylthio, alkenylthio, arylthio, and acyl. The alkyl group hasthe same meaning as defined above. The alkyl moiety of the alkoxy,acyloxy, alkoxycarbonyl, alkyl-substituted sulfamoyl, sulfonamido,alkyl-substituted carbamoyl, amido, alkylthio, and acyl groups may bethe same as the above alkyl group.

The alkenyl group has the same meaning as defined above. The alkenylmoiety of the alkenyloxy, acyloxy, alkenyloxycarbonyl,alkenyl-substituted sulfamoyl, sulfonamido, alkenyl-substitutedcarbamoyl, amido, alkenylthio, and acyl groups may be the same as theabove alkenyl group. Examples of the aryl group include phenyl,α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl,4-octyloxyphenyl, and 4-dodecyloxyphenyl. Examples of the aryl moiety ofthe aryloxy, acyloxy, aryloxycarbonyl, aryl-substituted sulfamoyl,sulfonamido, aryl-substituted carbamoyl, amido, arylthio, and acylgroups may be the same as those of the above aryl group.

When X¹, X² or X³ is —NR⁴—, —NR⁵—, or —NR⁶—, the heterocyclic grouprepresented by R⁴, R⁵ and R⁶ is preferably aromatic. The aromaticheterocycle is generally an unsaturated heterocycle, preferably aheterocycle having double bonds in the largest number. The heterocycleis preferably a five-, six- or seven-membered ring, more preferably afive- or six-membered ring, most preferably a six-membered ring. Thehetero atom of the heterocycle is preferably N, S or O, particularlypreferably N. The aromatic heterocycle is particularly preferably apyridine ring (in which the heterocyclic group is preferably 2-pyridylor 4-pyridyl). The heterocycle may have a substituent or substituents.Examples of the substituent of the heterocyclic group may be the same asthose of the substituent on the aryl moiety. When X¹, X² or X³ is asingle bond, the heterocyclic group preferably has a free atomic valenceon a nitrogen atom. The heterocyclic group having a free atomic valenceon a nitrogen atom is preferably a five-, six- or seven-membered ring,more preferably a five- or six-membered ring, most preferably afive-membered ring. The heterocyclic group may have two or more nitrogenatoms. The heterocyclic group may also have a hetero atom (e.g. O or S)other than the nitrogen atom. The heterocyclic group may have asubstituent or substituents. Examples of the substituent of theheterocyclic group may be the same as those of the substituent on thearyl moiety.

Preferred examples of the compound represented by formula (I) are shownbelow, but the invention is not meant to be limited to these.

The compound represented by formula (I) can be synthesized according tothe synthetic method as described, for example, in JP-A-2003-344655.

Next, the compound represented by formula (II) is described below.Ar¹-L¹

Ar²-L²

_(n)Ar³  Formula (II)

In formula (II), Ar¹, Ar² and Ar³ each independently represent an arylgroup or an aromatic heterocyclic group; L¹ and L² each independentlyrepresent a single bond or a divalent linking group; n represents aninteger of 3 or more; and a plurality of the Ar² moieties may be thesame or different, and a plurality of the L² moieties may be the same ordifferent.

Ar¹, Ar² or Ar³ represents an aryl group or an aromatic heterocycle. Thearyl group represented by Ar¹, Ar² or Ar³ is preferably an aryl group of6 to 30 carbon atoms, and may be a monocycle or condensed with any otherring(s) to form a condensed ring. If possible, the aryl group may have asubstituent or substituents, which may be the substituent T as describedlater.

In formula (II), the aryl group represented by Ar¹, Ar² or Ar³ is morepreferably of 6 to 20 carbon atoms, particularly preferably of 6 to 12carbon atoms, examples of which include phenyl, p-methylphenyl andnaphthyl.

In formula (II), the aromatic heterocycle represented by Ar¹, Ar² or Ar³may be any aromatic heterocycle having at least one of oxygen, nitrogenand sulfur atoms, and is preferably a five- or six-membered aromaticheterocycle having at least one of oxygen, nitrogen and sulfur atoms. Ifpossible, the aromatic heterocycle may have a substituent orsubstituents, which may be the substituent T as described later.

The aforementioned substituent T is explained below.

Examples of the substituent T include an alkyl group (preferably analkyl group having from 1 to 20, more preferably from 1 to 12, andparticularly preferably from 1 to 8 carbon atoms, e.g., methyl, ethyl,iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl,cyclopentyl, cyclohexyl), an alkenyl group (preferably an alkenyl grouphaving from 2 to 20, more preferably from 2 to 12, and particularlypreferably from 2 to 8 carbon atoms, e.g., vinyl, allyl, 2-butenyl,3-pentenyl), an alkynyl group (preferably an alkynyl group having from 2to 20, more preferably from 2 to 12, and particularly preferably from 2to 8 carbon atoms, e.g., propargyl, 3-pentynyl), an aryl group(preferably an aryl group having from 6 to 30, more preferably from 6 to20, and particularly preferably from 6 to 12 carbon atoms, e.g., phenyl,p-methylphenyl, naphthyl), a substituted or unsubstituted amino group(preferably an amino group having from 0 to 20, more preferably from 0to 10, and particularly preferably from 0 to 6 carbon atoms, e.g.,amino, methylamino, dimethylamino, diethylamino, dibenzylamino), analkoxy group (preferably an alkoxy group having from 1 to 20, morepreferably from 1 to 12, and particularly preferably from 1 to 8 carbonatoms, e.g., methoxy, ethoxy, butoxy), an aryloxy group (preferably anaryloxy group having from 6 to 20, more preferably from 6 to 16, andparticularly preferably from 6 to 12 carbon atoms, e.g., phenyloxy,2-naphthyloxy), an acyl group (preferably an acyl group having from 1 to20, more preferably from 1 to 16, and particularly preferably from 1 to12 carbon atoms, e.g., acetyl, benzoyl, formyl, pivaloyl), analkoxycarbonyl group (preferably an alkoxycarbonyl group having from 2to 20, more preferably from 2 to 16, and particularly preferably from 2to 12 carbon atoms, e.g., methoxycarbonyl, ethoxycarbonyl), anaryloxycarbonyl group (preferably an aryloxycarbonyl group having from 7to 20, more preferably from 7 to 16, and particularly preferably from 7to 10 carbon atoms, e.g., phenyloxycarbonyl), an acyloxy group(preferably an acyloxy group having from 2 to 20, more preferably from 2to 16, and particularly preferably from 2 to 10 carbon atoms, e.g.,acetoxy, benzoyloxy), an acylamino group (preferably an acylamino grouphaving from 2 to 20, more preferably from 2 to 16, and particularlypreferably from 2 to 10 carbon atoms, e.g., acetylamino, benzoylamino),an alkoxycarbonylamino group (preferably an alkoxycarbonylamino grouphaving from 2 to 20, more preferably from 2 to 16, and particularlypreferably from 2 to 12 carbon atoms, e.g., methoxycarbonylamino), anaryloxycarbonylamino group (preferably an aryloxycarbonylamino grouphaving from 7 to 20, more preferably from 7 to 16, and particularlypreferably from 7 to 12 carbon atoms, e.g., phenyloxycarbonylamino), asulfonylamino group (preferably a sulfonylamino group having from 1 to20, more preferably from 1 to 16, and particularly preferably from 1 to12 carbon atoms, e.g., methanesulfonylamino, benzenesulfonylamino), asulfamoyl group (preferably a sulfamoyl group having from 0 to 20, morepreferably from 0 to 16, and particularly preferably from 0 to 12 carbonatoms, e.g., sulfamoyl, methylsulfamoyl, dimethylsulfamoyl,phenylsulfamoyl), a carbamoyl group (preferably a carbamoyl group havingfrom 1 to 20, more preferably from 1 to 16, and particularly preferablyfrom 1 to 12 carbon atoms, e.g., carbamoyl, methylcarbamoyl,diethylcarbamoyl, phenylcarbamoyl), an alkylthio group (preferably analkylthio group having from 1 to 20, more preferably from 1 to 16, andparticularly preferably from 1 to 12 carbon atoms, e.g., methylthio,ethylthio), an arylthio group (preferably an arylthio group having from6 to 20, more preferably from 6 to 16, and particularly preferably from6 to 12 carbon atoms, e.g., phenylthio), a sulfonyl group (preferably asulfonyl group having from 1 to 20, more preferably from 1 to 16, andparticularly preferably from 1 to 12 carbon atoms, e.g., mesyl, tosyl),a sulfinyl group (preferably a sulfinyl group having from 1 to 20, morepreferably from 1 to 16, and particularly preferably from 1 to 12 carbonatoms, e.g., methanesulfinyl, benzenesulfinyl), a ureido group(preferably a ureido group having from 1 to 20, more preferably from 1to 16, and particularly preferably from 1 to 12 carbon atoms, e.g.,ureido, methylureido, phenylureido), a phosphoric acid amido group(preferably a phosphoric acid amido group having from 1 to 20, morepreferably from 1 to 16, and particularly preferably from 1 to 12 carbonatoms, e.g., diethylphosphoric acid amido, phenylphosphoric acid amido),a hydroxy group, a mercapto group, a halogen atom (e.g., fluorine,chlorine, bromine, or iodine atom), a cyano group, a sulfo group, acarboxyl group, a nitro group, a hydroxamic acid group, a sulfino group,a hydrazino group, an imino group, a heterocyclic group (preferably aheterocyclic group having from 1 to 30, and more preferably from 1 to 12carbon atoms; containing, as a hetero atom(s), for example, a nitrogenatom, an oxygen atom, or a sulfur atom, and specifically, e.g.,imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino,benzoxazolyl, benzimidazolyl, benzothiazolyl can be exemplified), and asilyl group (preferably a silyl group having 3 to 40, more preferably 3to 30, and particularly preferably 3 to 24 carbon atoms, e.g.trimethylsilyl, triphenylsilyl). These substituents may further besubstituted.

When there are two or more substituents, they may be the same ordifferent. The substituents may bond together, to form a ring, ifpossible.

Specific examples of the aromatic heterocycle represented by Ar¹, Ar² orAr³ in formula (II) include furan, pyrrole, thiophene, imidazole,pyrazole, pyridine, pyradine, pyridazine, triazole, triazine, indole,indazole, purin, thiazoline, thiazole, thiadiazole, oxazoline, oxazole,oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine,quinoxaline, quinazoline, cinnoline, pteridine, acridine,phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole,benzothiazole, benzotriazole, tetrazaindene, pyrrolotriazole, andpyrazolotriazole. The aromatic heterocycle is preferably benzimidazole,benzoxazole, benzothiazole, or benzotriazole.

In formula (II), L¹ or L² represents a single bond or a divalent linkinggroup. Preferred examples of the divalent linking group include a grouprepresented by —NR⁷—, in which R⁷ represents a hydrogen atom oroptionally substituted alkyl or aryl group; —SO₂—, —CO—, an alkylenegroup, a substituted alkylene group, an alkenylene group, a substitutedalkenylene group, an alkynylene group, —O—, —S—, —SO—, and a groupformed of a combination of two or more of these divalent groups. Amongthese divalent groups, —O—, —CO—, —SO₂NR⁷—, —NR⁷SO₂—, —CONR⁷—, —NR⁷CO—,—COO—, —COO—, and an alkynylene group are more preferred, and —CONR⁷—,—NR⁷CO—, —COO—, —COO—, and an alkynylene group are most preferred.

In the compound represented by formula (II) that can be used in thepresent invention, Ar² is linked to L¹ and L², and when Ar² is aphenylene group, L¹-Ar²-L² and L²-Ar²-L² each most preferably form apara position relationship (1,4-position relationship).

In formula (II), n represents an integer of 3 or more, preferably of 3to 7, more preferably of 3 to 5.

Specific examples of the compound represented by formula (II) are shownbelow, but the invention is not meant to be limited to these.

The compound represented by formula (II) can be synthesized by any ofknown methods. In the following, one of such methods will be explainedtaking Exemplified compound (II-41) as an example, but the invention isnot limited to this.

Synthetic Example 1 Synthesis of Exemplified Compound (II-41)

The exemplified compound (II-41) was synthesized in accordance with thefollowing scheme:

(Synthesis of Intermediate (S1))

To 500 ml of DMF, 67.3 g of methyl 2,4-dihydroxybenzoate, 85.3 ml of2-ethylhexylbromide, and 137.5 g of potassium carbonate were added, andthe resultant mixture was heated under stirring on a hot water bath for6 hours. Then, 75.9 ml of dimethyl sulfate and 137 g of potassiumcarbonate were added thereto, followed by heating under stirring furtherfor 10 hours. After the completion of the reaction, 500 ml of ethylacetate was added thereto, to separate inorganic salts by vacuumfiltration. The filtrate was admixed with water, and then the resultantorganic layer was extracted twice with ethyl acetate. The organic layerwas washed with 1N hydrochloric acid, water, and saturated brinesubsequently, then dried over magnesium carbonate. The solvent was thendistilled off under reduced pressure. The residue was purified by silicagel column chromatography (eluent: ethyl acetate/n-hexane= 1/10), togive 70 g of a methyl ester-form intermediate as an oily substance(yield 59%). The thus-obtained methyl ester-form intermediate wasdissolved in 150 ml of methanol and 143 ml of 5N potassium hydroxideaqueous solution, followed by heating under reflux for 2 hours. Then,the resultant mixture was poured into a mixed solution of 500 ml ofwater and 59.3 ml of 12N hydrochloric acid. Thereto, was added 500 ml ofethyl acetate, and the organic layer was extracted. The thus-obtainedorganic layer was subsequently washed with water and saturated brine,and dried over magnesium sulfate. The solvent was then distilled offunder reduced pressure, to give 66 g of Intermediate (S1) as an oilysubstance.

(Synthesis of Intermediate (S3))

28 g of Intermediate (S1), 100 mL of toluene, and 0.1 mL ofdimethylformamide were heated to 70° C. Then, to the resultant mixture,8.03 ml of thionyl chloride was slowly added dropwise, followed byheating under stirring at 70° C. for 1 hour. Then, to the resultantreaction liquid, was added a solution prepared in advance by dissolving13.81 g of 4-hydroxybenzoic acid (S2) in 20 mL of dimethylformamide.Then, the mixture was allowed to react at 70° C. for 2 hours. After thereaction, the reaction liquid was cooled to the room temperature, andethyl acetate and water were added thereto, to extract an organic layer.The organic layer was washed with 1N hydrochloric acid, water, andsaturated brine subsequently, then dried over magnesium sulfate. Thesolvent was then distilled off under reduced pressure. The residue waspurified by silica gel column chromatography (eluent: methylenechloride/methanol=20/1), followed by dispersing with n-hexane, and thenfiltration under reduced pressure, to give 21.8 g of Intermediate (S3)as a white solid substance.

(Synthesis of Exemplified Compound (II-41))

19.22 g of Intermediate (S3), 3.72 g of 4,4′-biphenol, and 0.98 g ofdimethylaminopyridine were dissolved in 75 ml of methylene chloride and25 ml of THF. Thereto, 10.73 g of dicyclohexyl carbodiimide was slowlyadded, and then, the resultant solution was heated under reflux for 3hours. Then, the reaction solution was cooled to room temperature, andthe thus-precipitated crystals (dicyclohexylurea) were separated byfiltration. The filtrate was admixed with water, and the organic layerwas separated. The organic layer was washed with 1N hydrochloric acid,water, and saturated brine subsequently, then dried over magnesiumsulfate. The solvent was then distilled off under reduced pressure. Theresidue was purified by silica gel column chromatography, and thenrecrystallized from methylene chloride/methanol, to give 6.4 g ofExemplified compound (II-41) as a white solid substance.

The thus-obtained compound was identified by ¹H-NMR (400 MHz).

¹H-NMR (CDCl₃): δ 0.89 (m, 12H), 1.28-1.60 (m, 16H), 1.76 (m, 2H), 3.92(m, 10H), 6.55 (m, 4H), 7.29 (d, 4H), 7.38 (d, 4H), 7.64 (d, 4H), 8.08(d, 2H), 8.29 (d, 4H)

The melting point of the obtained compound was 94° C.

Preferable examples of the compound exhibiting a Re/Rth ratio of 0.35 ormore, include those represented by formula (III).Ar¹¹-L¹²-X-L¹³-Ar¹²  Formula (III)

In formula (III), Ar¹¹ and Ar¹² each independently represent an aromaticgroup; L¹² and L¹³ each independently represent a divalent linking groupselected from the group consisting of alkylene groups, —O—, —CO—, andcombinations thereof; and X represents 1,4-cyclohexylene, vinylene, orethynylene.

In formula (III), L¹² and L¹³ each independently represent a divalentlinking group selected from the group consisting of an alkylene group,—O—, —CO—, and a combination thereof. An alkylene group having achain-like structure is preferred to a cyclic one. A linear alkylenegroup is further preferred to a branched chain-like one. The alkylenegroup preferably has from 1 to 10, more preferably from 1 to 8, furtherpreferably from 1 to 6, still further preferably from 1 to 4, and mostpreferably from 1 or 2 (methylene or ethylene) carbon atoms. It isparticularly preferable that L¹² and L¹³ are —O—CO— or —CO—O—.

In formula (III), X represents 1,4-cyclohexylene, vinylene orethynylene. X is preferably 1,4-cyclohexylene.

Ar¹¹ and Ar¹² each independently represent an aromatic group. The term“aromatic group” as referred to herein includes aryl groups (aromatichydrocarbon groups), substituted aryl groups, aromatic heterocyclicgroups, and substituted aromatic heterocyclic groups. An aryl group anda substituted aryl group are preferred to an aromatic heterocyclic groupand a substituted aromatic heterocyclic group. An aromatic heterocyclicgroup generally has an unsaturated heterocycle. It is preferable thatthe aromatic heterocycle is 5-, 6- or 7-membered ring and a 5- or6-membered ring is more preferable. In general, an aromatic heterocyclehas double bonds in the largest number. As a hetero atom, nitrogen,oxygen and sulfur atoms are preferable and a nitrogen atom or sulfuratom is particularly preferable. Examples of the aromatic heterocycleinclude furan ring, thiophene ring, pyrrole ring, oxazole ring,isoxazole ring, thiazole ring, isothiazole ring, imidazole ring,pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring,pyridazine ring, pyrimidine ring, pyrazine ring, and 1,3,5-triazinering. Preferred aromatic rings of the aromatic groups are benzene ring,furan ring, thiophene ring, pyrrole ring, oxazole ring, thiazole ring,imidazole ring, triazole ring, pyridine ring, pyrimidine ring, andpyrazine ring, and benzene ring is particularly preferred.

Examples of the substituent in the substituted aryl group andsubstituted aromatic heterocyclic group include halogen atoms (F, Cl, Brand I), hydroxyl group, carboxyl group, cyano group, amino group,alkylamino groups (for example, methylamino, ethylamino, butylamino anddimethylamino groups), nitro group, sulfo group, carbamoyl group,alkylcarbamoyl groups (for example, N-methylcarbamoyl, N-ethylcarbamoyland N,N-dimethylcarbamoyl groups), sulfamoyl group, alkylsulfamoylgroups (for example, N-methylsulfamoyl, N-ethylsulfamoyl and N,N-dimethylsulfamoyl groups), ureido group, alkylureido groups (forexample, N-methylureido, N,N-dimethylureido and N,N,N′-trimethylureidogroups), alkyl groups (for example, methyl, ethyl, propyl, butyl,pentyl, heptyl, octyl, isopropyl, s-butyl, t-amyl, cyclohexyl andcyclopentyl groups), alkenyl groups (for example, vinyl, allyl andhexenyl groups), alkynyl groups (for example, ethynyl and butynylgroups), acyl groups (for example, formyl, acetyl, butyryl, hexanoyl andlauryl groups), acyloxy groups (for example, acetoxy, butyryloxy,hexanoyloxy and lauryloxy groups), alkoxy groups (for example, methoxy,ethoxy, propoxy, butoxy, pentyloxy, heptyloxy and octyloxy groups),aryloxy groups (for example, phenoxy group), alkoxycarbonyl groups (forexample, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,butoxycarbonyl, pentyloxycarbonyl and heptyloxycarbonyl groups),aryloxycarbonyl groups (for example, phenoxycarbonyl group),alkoxycarbonylamino groups (for example, butoxycarbonylamino andhexyloxycarbonylamino groups), alkylthio groups (for example,methylthio, ethylthio, propylthio, butylthio, pentylthio, heptylthio andoctylthio groups), arylthio groups (for example, phenylthio group),alkylsulfonyl groups (for example, methylsulfonyl, ethylsulfonyl,propylsulfonyl, butylsulfonyl, pentylsulfonyl, heptylsulfonyl andoctylsulfonyl groups), amido groups (for example, acetamido, butylamido,hexylamido and laurylamido groups), and non-aromatic heterocyclic groups(for example, morpholyl and pyradinyl groups).

Preferable examples of the substituent in the substituted aryl group andsubstituted aromatic heterocyclic group include halogen atom, cyanogroup, carboxyl group, hydroxyl group, amino group, alkyl-substitutedamino group, acyl group, acyloxy group, amido group, alkoxycarbonylgroup, alkoxy group, alkylthio group, and alkyl group. In the alkylaminogroups, alkoxycarbonyl groups, alkoxy groups and alkylthio groups, eachalkyl moiety and alkyl group may further have a substituent. Examples ofthe substituent on the alkyl moiety and alkyl group include halogenatom, hydroxyl, carboxyl, cyano, amino, alkylamino group, nitro, sulfo,carbamoyl, alkylcarbamoyl group, sulfamoyl, alkylsulfamoyl group,ureido, alkylureido group, alkenyl group, alkynyl group, acyl group,acyloxy group, acylamino group, alkoxy group, aryloxy group,alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group,alkylthio group, arylthio group, alkylsulfonyl group, amido group, andnon-aromatic heterocyclic group. Preferable examples of the substituenton the alkyl moiety and alkyl group include halogen atom, hydroxyl,amino, alkylamino group, acyl group, acyloxy group, acylamino group,alkoxycarbonyl group, and alkoxy group.

Specific examples of the compound represented by formula (III) are shownbelow, but the invention is not meant to be limited to these.

Other examples of the compound exhibiting a Re/Rth ratio of less than0.35 or not less than 0.35, include compounds represented by formula(IV).

In the following, the compound represented by formula (IV) will beexplained.

In formula (IV), R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ each independently representa hydrogen atom or a substituent.

Examples of the substituent represented by R⁴, R⁵, R⁶, R⁷, R⁸, or R⁹include an alkyl group (preferably an alkyl group having from 1 to 40,more preferably from 1 to 30, and particularly preferably from 1 to 20carbon atoms, e.g., methyl, ethyl, iso-propyl, tert-butyl, n-octyl,n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl), an alkenylgroup (preferably an alkenyl group having from 2 to 40, more preferablyfrom 2 to 30, and particularly preferably from 2 to 20 carbon atoms,e.g., vinyl, allyl, 2-butenyl, 3-pentenyl), an alkynyl group (preferablyan alkynyl group having from 2 to 40, more preferably from 2 to 30, andparticularly preferably from 2 to 20 carbon atoms, e.g., propargyl,3-pentynyl), an aryl group (preferably an aryl group having from 6 to30, more preferably from 6 to 20, and particularly preferably from 6 to12 carbon atoms, e.g., phenyl, p-methylphenyl, naphthyl), a substitutedor unsubstituted amino group (preferably an amino group having from 0 to40, more preferably from 0 to 30, and particularly preferably from 0 to20 carbon atoms, e.g., unsubstituted amino, methylamino, dimethylamino,diethylamino, anilino), an alkoxy group (preferably an alkoxy grouphaving from 1 to 40, more preferably from 1 to 30, and particularlypreferably from 1 to 20 carbon atoms, e.g., methoxy, ethoxy, butoxy), anaryloxy group (preferably an aryloxy group having from 6 to 40, morepreferably from 6 to 30, and particularly preferably from 6 to 20 carbonatoms, e.g., phenyloxy, 2-naphthyloxy), an acyl group (preferably anacyl group having from 1 to 40, more preferably from 1 to 30, andparticularly preferably from 1 to 20 carbon atoms, e.g., acetyl,benzoyl, formyl, pivaloyl), an alkoxycarbonyl group (preferably analkoxycarbonyl group having from 2 to 40, more preferably from 2 to 30,and particularly preferably from 2 to 20 carbon atoms, e.g.,methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl group (preferablyan aryloxycarbonyl group having from 7 to 40, more preferably from 7 to30, and particularly preferably from 7 to 20 carbon atoms, e.g.,phenyloxycarbonyl), an acyloxy group (preferably an acyloxy group havingfrom 2 to 40, more preferably from 2 to 30, and particularly preferablyfrom 2 to 20 carbon atoms, e.g., acetoxy, benzoyloxy), an acylaminogroup (preferably an acylamino group having from 2 to 40, morepreferably from 2 to 30, and particularly preferably from 2 to 20 carbonatoms, e.g., acetylamino, benzoylamino), an alkoxycarbonylamino group(preferably an alkoxycarbonylamino group having from 2 to 40, morepreferably from 2 to 30, and particularly preferably from 2 to 20 carbonatoms, e.g., methoxycarbonylamino), an aryloxycarbonylamino group(preferably an aryloxycarbonylamino group having from 7 to 40, morepreferably from 7 to 30, and particularly preferably from 7 to 20 carbonatoms, e.g., phenyloxycarbonylamino), a sulfonylamino group (preferablya sulfonylamino group having from 1 to 40, more preferably from 1 to 30,and particularly preferably from 1 to 20 carbon atoms, e.g.,methanesulfonylamino, benzenesulfonylamino), a sulfamoyl group(preferably a sulfamoyl group having from 0 to 40, more preferably from0 to 30, and particularly preferably from 0 to 20 carbon atoms, e.g., itsulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl), acarbamoyl group (preferably a carbamoyl group having from 1 to 40, morepreferably from 1 to 30, and particularly preferably from 1 to 20 carbonatoms, e.g., unsubstituted carbamoyl, methylcarbamoyl, diethylcarbamoyl,phenylcarbamoyl), an alkylthio group (preferably an alkylthio grouphaving from 1 to 40, more preferably from 1 to 30, and particularlypreferably from 1 to 20 carbon atoms, e.g., phenylthio), a sulfonylgroup (preferably a sulfonyl group having from 1 to 40, more preferablyfrom 1 to 30, and particularly preferably from 1 to 20 carbon atoms,e.g., mesyl, tosyl), a sulfinyl group (preferably a sulfinyl grouphaving from 1 to 40, more preferably from 1 to 30, and particularlypreferably from 1 to 20 carbon atoms, e.g., methanesulfinyl,benzenesulfinyl), a ureido group (preferably a ureido group having from1 to 40, more preferably from 1 to 30, and particularly preferably from1 to 20 carbon atoms, e.g., unsubstituted ureido; methylureido,phenylureido), a phosphoric acid amido group (preferably a phosphoricacid amido group having from 1 to 40, more preferably from 1 to 30, andparticularly preferably from 1 to 20 carbon atoms, e.g.,diethylphosphoric acid amido, phenylphosphoric acid amido), a hydroxygroup, a mercapto group, a halogen atom (e.g., fluorine, chlorine,bromine, or iodine atom), a cyano group, a sulfo group, a carboxylgroup, a nitro group, a hydroxamic acid group, a sulfino group, ahydrazino group, an imino group, a heterocyclic group (preferably aheterocyclic group having from 1 to 30, and more preferably from 1 to 12carbon atoms; containing, as a hetero atom(s), for example, a nitrogenatom, an oxygen atom, or a sulfur atom, and specifically, e.g.,imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino,benzoxazolyl, benzimidazolyl, benzothiazolyl, and 1,3,5-triazinyl can beexemplified), and a silyl group (preferably a silyl group having 3 to40, more preferably 3 to 30, and particularly preferably 3 to 24 carbonatoms, e.g. trimethylsilyl, triphenylsilyl). These substituents mayfurther be substituted by any of these groups or atoms. When there aretwo or more substituents, they may be the same or different. Thesubstituents may bond together, to form a ring, if possible.

Preferred examples of the substituent represented by R⁴, R⁵, R⁶, R⁷, R⁸,or R⁹, include an alkyl group, an aryl group, a substituted orunsubstituted amino group, an alkoxy group, an alkylthio group, or ahalogen atom.

Specific examples of the compound represented by formula (IV) are shownbelow, but the present invention is not limited to these.

The above compound can be used in an amount of generally 0.01 to 20 massparts, preferably 1 to 10 mass parts, to 100 mass parts of the celluloseacetate.

The compound exhibiting a Re/Rth ratio of less than 0.35 and thecompound exhibiting a Re/Rth ratio of not less than 0.35 are preferablymixed at a mixing ratio in terms of mass of the former compound to thelater compound in the range of 1:9 to 9:1, more preferably of 2:8 to8:2.

The compound represented by formula (IV) can be synthesized according tothe synthetic method as described, for example, in JP-A-2005-134884.

(Production of Cellulose Acetate Film)

The cellulose acylate film is preferably prepared according to a solventcast method. In the solvent cast method, a solution (dope) in which acellulose acylate is dissolved in an organic solvent is used, to preparea film.

The organic solvent preferably comprises a solvent selected from anether having 3 to 12 carbon atoms, an alcohol having 1 to 6 carbonatoms, a ketone having 3 to 12 carbon atoms, an ester having 3 to 12carbon atoms, and a halogenated hydrocarbon having 1 to 6 carbon atoms.

The ether, ketone, and ester each may have a cyclic structure. Acompound having two or more functional groups of ether, ketone or ester(i.e. —O—, —CO— or —COO—) is also usable as the solvent. The organicsolvent may have another functional group. When the organic solvent is acompound having two or more functional groups, the number of carbonatoms is in any of the above ranges defined for the compound having anyof the functional groups.

Examples of the ether having 3 to 12 carbon atoms include diisopropylether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane,tetrahydrofuran, anisole, and phenetole.

Examples of the alcohol having 1 to 6 carbon atoms include methanol,ethanol, 2-propanol, 1-butanol, and 2-butanol.

Examples of the ketone having 3 to 12 carbon atoms include acetone,methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone,and methylcyclohexane.

Examples of the ester having 3 to 12 carbon atoms include ethyl formate,propyl formate, pentyl formate, methyl acetate, ethyl acetate, andpentyl acetate.

Examples of the organic solvent having two or more kinds of functionalgroups include 2-ethoxyethyl acetate, 2-methoxyethanol, and2-butoxyethanol.

The halogenated hydrocarbon preferably has one or two carbon atoms,particularly preferably one carbon atom. The halogen in the halogenatedhydrocarbon is preferably chlorine. The ratio that a hydrogen atom inthe halogenated hydrocarbon is substituted with a halogen is preferably25 to 75 mol %, more preferably 30 to 70 mol %, further preferably 35 to65 mol %, most preferably 40 to 60 mol %. A typical halogenatedhydrocarbon is methylene chloride.

Two or more kinds of the organic solvents may be mixed to use incombination. Examples of the solvent that can be preferably used in thepresent invention, include a mixed solvent of methylene chloride andmethanol.

It is preferable that the cellulose acylate for use in the presentinvention is in a form of a solution in which cellulose acylate isdissolved in an organic solvent at a concentration of from 10 to 30% bymass, more preferably from 13 to 27% by mass, and particularlypreferably from 15 to 25% by mass. The cellulose acylate concentrationmay be controlled to such a level, by controlling the concentration atthe dissolution step. Alternatively, it is also possible that a solutionof a low concentration (for example, from 9 to 14% by mass) ispreliminarily prepared and then the concentration is controlled to theaforementioned high level in the subsequent concentrating step as willbe described hereinafter. It is also possible that a cellulose acylatesolution of a high concentration is preliminarily prepared and thenvarious additives are added to give a cellulose acylate solution of alowered concentration as mentioned in the above. Any method may be usedwithout any problem so long as the cellulose acylate solution of theaforementioned concentration preferably in the present invention can beattained.

It is preferable in the present invention that a diluted celluloseacylate solution, that is obtained by diluting the cellulose acylatesolution with the organic solvent of the same composition to give aconcentration of from 0.1 to 5% by mass, has a cellulose acylateaggregate molecular weight of from 150,000 to 15,000,000, morepreferably from 180,000 to 9,000,000. This aggregate molecular weightcan be determined by a static light scattering method. It is preferableto make the solution to give an inertia square radius, which iddetermined at the same time, of from 10 to 200 nm, more preferably from20 to 200 nm. It is also preferable to make the solution to give asecond virial coefficient of from −2×10⁻⁴ to +4×10⁻⁴, more preferablyfrom −2×10⁻⁴ to +2×10⁻⁴. Next, the definitions of the aggregatemolecular weight, inertia square radium, and second virial coefficientas referred to herein will be illustrated.

These items can be measured by using a static light scattering method inaccordance with the following procedures. Although the measurement iscarried out in a dilute region as a matter of convenience in anmeasuring apparatus, these data reflect behaviors of the dope in thehigh concentration region according to the present invention. First,cellulose acylate is dissolved in a solvent to be used in the dope, togive solutions having concentrations of 0.1% by mass, 0.2% by mass, 0.3%by mass, and 0.4% by mass, respectively. To prevent water absorption,cellulose acylate having been dried at 120° C. for 2 hours is employedand weighed at 25° C. under 10% RH. Dissolution is carried out inaccordance with the method employed in dissolving the dope (e.g. aroom-temperature dissolution method, a cold dissolution method, a hotdissolution method).

Then, these solutions and solvents are filtered through a 0.2-μm filtermade of Teflon (registered trademark). Then, static light scattering ofeach solution thus filtered is measured at 25° C. at from 30° to 140° atthe intervals of 10°, by using a light scattering meter (Model DLS-700,trade name, manufactured by OTUKA ELECTRONICS CO., LTD.). The obtaineddata are then analyzed by the BERRY plot method. As the refractive indexrequired in the analysis, use is made of the value of the solventdetermined by using an ABBE refraction system. The concentrationgradient (dn/dc) of the refractive index is measured with a differentialrefractometer (Model DRM-1021, trade name, manufactured by OTUKAELECTRONICS CO., LTD.), by using the solvents and solutions employed inmeasuring light scattering.

Next, the preparation of a cellulose acylate solution (dope) that can beused in the present invention will be illustrated. The cellulose acylateis dissolved by an arbitrary method without particular limitation, i.e.,by a room-temperature dissolution method, a cold dissolution method, ahot dissolution method, or a combination thereof. Regarding those,methods of preparing cellulose acylate solutions are described, forexample, in JP-A-5-163301, JP-A-61-106628, JP-A-58-127737, JP-A-9-95544,JP-A-10-95854, JP-A-10-45950, JP-A-2000-53784, JP-A-11-322946,JP-A-11-322947, JP-A-2-276830, JP-A-2000-273239, JP-A-11-71463,JP-A-04-259511, JP-A-2000-273184, JP-A-11-323017 and JP-A-11-302388.These techniques of dissolving cellulose acylate in organic solvents asdescribed above are appropriately applicable in the present inventionwithin the scope of the invention.

These techniques can be carried out, in particular for a systemutilizing a non-chlorine-containing solvent, in accordance with themethod described in detail in Japan Institute of Invention andInnovation Journal of Technical Disclosure No. 2001-1745 (Mar. 15, 2001,Japan Institute of Invention and Innovation), pages 22 to 25. Further,the cellulose acylate dope solution according to the present inventionis usually concentrated and filtered, as described in detail in JapanInstitute of Invention and Innovation Journal of Technical DisclosureNo. 2001-1745 (Mar. 15, 2001, Japan Institute of Invention andInnovation), p. 25. In hot dissolution, a temperature not lower than theboiling point of the organic solvent to be employed is used in mostcases, and the dissolution is performed under pressurized condition insuch cases.

(Cellulose Derivative Film)

In the below, described will be the method of producing the opticalcompensation film of the present invention (herein also referred to asthe cellulose acylate film, e.g. cellulose acetate film, of the presentinvention; and herein, the term cellulose acetate film may be utilizedin place of the cellulose acylate film in some cases).

As a method and apparatus for producing the cellulose acylate film ofthe present invention, use can be made of the solvent cast film-formingmethod and solvent cast film-forming apparatus conventionally employedin forming cellulose triacetate film. A dope (a cellulose acylatesolution) prepared in a dissolution machine (pot) is once stored in astorage pot, and, after defoaming, the dope is subjected to the finalpreparation. Then, the dope is discharged from a dope exhaust and fedinto a pressure die via, for example, a pressure constant-rate gear pumpwhereby the dope can be fed at a constant flow rate at a high accuracydepending on a rotational speed. From a pipe sleeve (slit) of thepressure die, the dope is uniformly cast onto a metallic supportcontinuously running in the casting section. At the peeling point wherethe metallic support has almost rounded in one cycle, the half-drieddope film (also called a web) is peeled from the metallic support.

The obtained web is clipped at both ends and dried by conveying with atenter while maintaining the width at a constant level. Subsequently, itis conveyed with rolls in a dryer to terminate the drying, and thenwound with a winder in a given length. Combination of the tenter and therolls in the dryer may vary depending on the purpose. In the solventcast film-forming method to produce a functional protective film forelectronic displays or silver halide photographic light-sensitivematerials, a coater is additionally employed in many cases, in additionto the solvent cast film-forming apparatus, so as to treat the filmsurface by providing, for example, an undercoat layer, an antistaticlayer, an anti-halation layer or a protective layer. These productionsteps are described in detail in ‘Hatsumei Kyokai Koukai Giho’ (Journalof Technical Disclosure) (Technical Disclosure No. 2001-1745, publishedMar. 15, 2001, Japan Institute of Invention and Innovation), pp. 25 to30, and they are classified into casting (including cocasting), metalsupport, drying, releasing (peeling), stretching, etc.

In the present invention, the space temperature of the casting sectionis not particularly limited, but it is preferably −50° C. to 50° C.,more preferably −30° C. to 40° C., and particularly preferably −20° C.to 30° C. In particular, a cellulose acylate solution that is cast at alow space temperature is instantaneously cooled on the support, thusincreasing the gel strength and thereby holding the film, which containsan organic solvent. By so doing, it is possible to peel the celluloseacylate from the support in a short period of time, without evaporatingthe organic solvent, thus enabling high speed casting to be achieved.With regard to means for space cooling, normal air, nitrogen, argon,helium, etc. may be employed, and the means is not particularly limited.In this case, the humidity is preferably 0% RH to 70% RH, and morepreferably 0% RH to 50% RH. Further, in the present invention, thetemperature of the support of the casting section, in which thecellulose acylate solution is to be cast, is generally −50° C. to 130°C., preferably −30° C. to 25° C., and more preferably −20° C. to 15° C.To maintain the casting section at the temperature preferably in thepresent invention, a cooled gas may be introduced to the castingsection, or a cooling device may be disposed in the casting section soas to cool the space. In this arrangement, it is important thatattention is paid to preventing water from becoming attached, and thiscan be achieved by a method utilizing a dried gas.

Particularly preferred contents and casting of each layer in the presentinvention are as follows. That is, the cellulose acylate solutioncontains, at 25° C., at least one type of liquid or solid plasticizer at0.1 to 20 mass % to the cellulose acylate, and/or at least one type ofliquid or solid ultraviolet absorbing agent at 0.001 to 5 mass % to thecellulose acylate, and/or at least one type of solid fine-particulatepowder having an average particle diameter of 5 to 3,000 nm at 0.001 to5 mass % to the cellulose acylate, and/or at least one type offluorine-containing surfactant at 0.001 to 2 mass % to the celluloseacylate, and/or at least one type of peeling agent at 0.0001 to 2 mass %to the cellulose acylate, and/or at least one type of degradationinhibitor at 0.0001 to 2 mass % to the cellulose acylate, and/or atleast one type of optical anisotropy control agent at 0.1 to 15 mass %to the cellulose acylate, and/or at least one type of infrared absorbingagent at 0.1 to 5 mass % to the cellulose acylate, and a celluloseacylate film prepared using the cellulose acylate solution above.

In the casting step, a single type of a cellulose acylate solution maybe cast to form a monolayer, or two or more types of cellulose acylatesolutions may be simultaneously or sequentially cocast. When two or morelayers are formed in the casting step, the cellulose acylate solutionsand the cellulose acylate film that are to be prepared from saidsolutions, are preferably provided in such a manner that: thechlorine-containing solvents in the respective layers have either thesame or different compositions; the respective layers contain either asingle type of additive or a mixture of two or more types of additives;the additives are placed in either the same or different layers; thesolutions of the additive for the respective layers have either the sameor different concentrations; aggregates or associations in therespective layers have either the same or different molecular weights;the solutions for the respective layers have either the same ordifferent temperatures; the respective layers are either the same ordifferent in coated amounts; the respective layers have either the sameor different viscosities; the respective layers have either the same ordifferent film thicknesses after drying; the states or distributions ofa material present in the respective layers are either the same ordifferent; the respective layers have either the same or differentphysical properties; or the respective layers have either uniformphysical properties or different physical properties distributed betweenthe layers.

In the cellulose acylate film, a plasticizer may be added, to improvethe mechanical properties or increase the drying speed. As theplasticizer, a phosphoric acid ester or a carboxylic acid ester can beused. Examples of the phosphate ester include triphenyl phosphate (TPP)and tricresyl phosphate (TCP).

Representative examples of the carboxylate ester include a phthalate anda citrate. Examples of the phthalate include dimethyl phthalate (DMP),diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate(DOP), diphenyl phthalate (DPP), and diethylhexyl phthalate (DEHP).Examples of the citrate include triethyl O-acetylcitrate (OACTE), andtributyl O-acetylcitrate (OACTB). Examples of other carboxylate esterinclude butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, andvarious trimellitic acid esters. A phthalate-series plasticizer (e.g.DMP, DEP, DBP, DOP, DPP, or DEHP) can be preferably used, and DEP andDPP are particularly preferred.

The amount of the plasticizer to be added is preferably from 0.1 to 25mass %, more preferably from 1 to 20 mass %, and most preferably 3 to 15mass %, to the amount of the cellulose ester.

To the cellulose acetate film, a deterioration inhibitor (for example,an antioxidant, a peroxide decomposer, a radical inhibitor, a metaldeactivator, an acid trapping agent, an amine) may be added. Thedeterioration inhibitor is described in JP-A-3-199201, JP-A-5-197073,JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. The amount of thedeterioration inhibitor to be added is preferably from 0.01 to 1 mass %,more preferably from 0.01 to 0.2 mass %, to the solution (dope) to beprepared, from the viewpoint of exhibiting the effect of deteriorationinhibitor or preventing the deterioration inhibitor from bleeding outonto the film surface. Examples of a particularly preferabledeterioration inhibitor include butylated hydroxytoluene (BHT), andtribenzyl amines (TBA).

(Orientation (Stretching) of Cellulose Acylate Film)

The cellulose acetate film may be subjected to stretching to adjust theretardation. The stretch ratio is preferably 3 to 100%. As thestretching method, any method may be used within the scope of thepresent invention, but, in particular, a tenter stretching is preferablyused from the viewpoint of in-plane uniformity. The width of thecellulose acylate film of the present invention is preferably at least100 cm or more. The dispersion (scattering) of a Re value in the totalwidth is preferably ±5 nm, and more preferably ±3 nm. Also, thedispersion of a Rth value is preferably ±10 nm, and more preferably ±5nm. Also, each dispersion of Re value and Rth value in a longitudinaldirection is preferably within the range of the dispersion in thetransverse direction.

Also, the stretching may be carried out in the course of film-forming,or a roll of a raw film wound after film-forming may be stretched. Inthe former case, the raw film may be stretched in the state of the filmcontaining a residual solvent(s). The amount of the residual solvent atthe start of the stretching is preferably 2 to 50%. The amount of theresidual solvent at the start of the stretching means the amount ofresidual solvent when both ends of a web (half-dried dope) starts to befastened with a clip, in the case of a tenter stretching method. It ismore preferable to start stretching when the amount of residual solventis 5 to 50%, and it is particularly preferable to start stretching whenthe amount of residual solvent is 10 to 45%. The amount of residualsolvent is calculated according to the following expression:(Amount of residual solvent)=100×{(Amount of solvent in web)/(Totalamount of the web)}

At that time, preferably, the film is stretched in a directionperpendicular to the longitudinal direction with conveying the film inthe longitudinal direction so that the slow axis of the film beperpendicular to the longitudinal direction of the film.

As to the stretching temperature, a proper condition may be selected,according to the film thickness and the amount of residual solvent atthe time of stretching.

In the case of stretching in the state that the film contain residualsolvent, it is preferable to dry the film after stretched. As to adrying method, the film may be dried, according to the aforementionedfilm-forming method.

The thickness (dry film thickness) of the cellulose acetate film afterstretched is generally 110 μm or less, preferably 40 to 110 μm, morepreferably 60 to 110 μm, and most preferably 80 to 110 μm. This filmthickness corresponds to the film thickness of the optical compensationsheet of the present invention.

(Wavelength Dispersion of Cellulose Acylate Film)

An example of performance required for an optical compensation sheet,can be mentioned forms of the wavelength dispersion of a Re retardationvalue and Rth retardation value. Because the optical compensation sheetworks as a negative retarder to compensate a liquid crystal, which is apositive retarder, it is necessary that the Rth retardation valuewavelength dispersion form of the optical compensation sheet be similarto the wavelength dispersion form of the liquid crystal, to compensate apolarizing light in the entire wavelength region of the visible light.At present, it is known that most of the wavelength dispersion form of aliquid crystal sealed in a liquid crystal cell is forward dispersion,and it is preferable that the Re retardation value and Rth retardationvalue wavelength dispersion forms of the optical compensation sheet be,respectively, a forward dispersion form. Specifically, a difference(Re700-Re400) between the Re retardation value (Re700) at a wavelengthof 700 nm and the Re retardation value (Re400) at a wavelength of 400 nmis preferably −25 nm to 10 nm, more preferably −25 nm to 5 nm. Also, adifference (Rth700-Rth400) between the Rth retardation value (Rth700) ata wavelength of 700 nm and the Rth retardation value (Rth400) at awavelength of 400 nm is preferably −50 nm to 20 nm, particularlypreferably −50 nm to 10 nm.

(Humidity Dependency of Re Retardation Value and Rth Retardation Value)

The Re Retardation value and Rth retardation value are preferably thosewhose change due to the environmental humidity is small.

A difference between the Re retardation value and Rth retardation valuemeasured in the environment of 25° C. and 10% RH and the Re retardationvalue and Rth retardation value measured in the environment of 25° C.and 80% RH, namely (Re10%-Re80% (25° C.)) and (Rth10%-Rth80% (25° C.))are also preferably small, and these values are preferably within 25 nmand within 70 nm, respectively. Also, it is more preferable that(Re10%-Re80% (25° C.)) be within 15 nm, and (Rth10%-Rth80% (25° C.)) bewithin 50 nm, and it is particularly preferable that (Re10%-Re80% (25°C.)) be within 10 nm, and (Rth10%-Rth80% (25° C.)) be within 40 nm.

(Moisture Permeability)

In the present invention, the moisture permeability of the celluloseacylate film may be found in the following manner: For example, thehumidity of a 70-mmφ sample is controlled in the condition of 25° C. and90% RH for 24 hours, and the sample is then subjected to a moisturepermeability tester (trade name: KK-709007, manufactured by Toyo SeikiSeisaku-sho, Ltd.), to calculate a water content per unit area (g/m²),according to JIS Z-0208, by using the following expression:(Moisture permeability)=(Mass after moisture conditioning)−(Mass beforemoisture conditioning)

The moisture permeability of the film as measured in the aforementionedmanner, is preferably 20 g/m²·24-hr to 250 g/m²·24-hr, and particularlypreferably 20 g/m²·24-hr to 230 g/m²·24-hr.

(Rate of Dimensional Change)

In the present invention, the rate of dimensional change may be found,for example, in the following manner: Each three test pieces of width 30mm and length 120 mm are cut from a sample, in the longitudinal (MD) andtransverse (TD) directions of said sample, respectively. A 6-mm (I) holeis punched in each end of the test piece at an interval of 100 mm byusing a punch. The humidity of the test piece is controlled in a roomkept at a temperature of 23±3° C. under a relative humidity of 65±5% for2 hours or more. The full scale (L 1) of the distance between thesepunched holes is measured, using an automatic pin gauge (manufactured byShinto Scientific Co., Ltd.), to the minimum scale of the order of1/1,000 mm. Then, the test piece is hung in a thermostat kept at 90°C.±1° C., to carry out heat treatment for 24 hours. The humidity of thetest piece is controlled in a room kept at 23±3° C. under a relativehumidity of 65±5% for 2 hours or more. Then, the distance (L²) betweenthe punched holes after the heat treatment is measured by the automaticpin gauge, to calculate a dimensional change, according to the followingexpression:Rate of dimensional change={(L1-L2)/L1}×100

The rate of dimensional change of the film of the present invention asmeasured in the aforementioned manner, is preferably 0.5% or less, morepreferably 0.3% or less.

(Rate of Dimensional Change Under High Humidity)

In the present invention, the rate of dimensional change under highhumidity may be found, for example, in the following manner: Each threetest pieces of width 30 mm and length 120 mm are cut from a sample, inthe longitudinal (MD) and transverse (TD) directions of said sample,respectively. A 6-mm (I) hole is punched in each end of the test pieceat an interval of 100 mm by using a punch. The humidity of the testpiece is controlled in a room kept at a temperature of 23±3° C. under arelative humidity of 65±5% for 2 hours or more. The full scale (L1) ofthe distance between these punched holes is measured, using an automaticpin gauge (manufactured by Shinto Scientific Co., Ltd.), to the minimumscale of the order of 1/1,000 mm. Then, the test piece is hung in athermohygrostat kept at 60° C.±1° C. under a relative humidity of 90±5%,to carry out heat treatment for 24 hours. The humidity of the test pieceis controlled in a room kept at 23±3° C. under a relative humidity of65±5% for 2 hours or more. Then, the distance (L3) between the punchedholes after the heat treatment is measured by the automatic pin gauge,to calculate a dimensional change under high humidity, according to thefollowing expression:Rate of dimensional change={(L1-L3)/L1}×100

The dimensional changes in 90° C. dry conditions and in 60° C./90% RHconditions as measured in the aforementioned manner, are both preferablyto be small, and they are preferably within −0.2%, more preferablywithin −0.15%.

(Surface Treatment of Cellulose Acetate Film)

To attain the surface energy of the cellulose acetate film within therange of 55 to 75 mN/m, it is preferable to carry out a surfacetreatment. Examples of the surface treatment include a saponificationtreatment, a plasma treatment, a flame treatment, and an ultravioletradiation treatment. The saponification treatment includes an acidsaponification treatment and an alkali saponification treatment. Theplasma treatment includes a corona discharge treatment and a glowdischarge treatment. To retain the flatness of the film, the temperatureof the cellulose acetate film in the surface treatment is kept to bepreferably lower than the glass transition temperature (Tg),specifically 150° C. or less. The surface energy of the celluloseacetate film after the surface treatment is preferably 55 to 75 mN/m.

The glow discharge treatment may be a treatment with low-temperatureplasma (thermal plasma) generated in a low-pressure gas of 10⁻³ to 20Torr. A treatment with plasma under the atmospheric pressure is alsopreferable. A plasma excitation gas is a gas, which can be excited toplasma under conditions as described above, and examples thereof includeargon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, flonse.g. tetrafluoromethane, and a mixture thereof. Details thereof aredescribed in “Kokai Giho of Japan Institute of Invention & Innovation”(Kogi No. 2001-1745, published on Mar. 15, 2001), pp. 30-32. In theplasma treatment under the atmospheric pressure, to which attention hasbeen paid in recent years, for example, a radiating energy of 20 to 500kGy is used under a condition of 10 to 1,000 keV, and preferably aradiating energy of 20 to 300 kGy is used under a condition of 30 to 500keV. Among these treatments, an alkali saponifying treatment isparticularly preferable, which treatment is quite effective as thesurface treatment for the cellulose acylate film.

The alkali saponifying treatment is preferably conducted, by directlyimmersing the cellulose acylate film into a bath of a saponifyingsolution, or by applying a saponifying solution onto the celluloseacylate film. Examples of the application method include a dip coatingmethod, a curtain coating method, an extrusion coating method, a barcoating method, and an E-type coating method. As the solvent in thealkali saponifying treatment coating solution, it is preferable toemploy a solvent, which has an excellent wettability appropriate forapplying the saponifying solution to a transparent support, and whichcan hold a favorable surface state without forming any irregularity onthe transparent support surface. More specifically, it is preferable touse an alcoholic solvent, and isopropyl alcohol is particularlypreferable. It is also possible to employ an aqueous solution of asurfactant as the solvent. As the alkali in the alkali-saponificationcoating solution, it is preferable to use an alkali soluble in theabove-described solvent, and KOH or/and NaOH is further preferable. Itis preferable that the saponification coating solution has a pH value of10 or higher, more preferably 12 or higher. Regarding the reactionconditions, it is preferable to perform the alkali saponification atroom temperature for 1 second or longer but 5 minutes or shorter, morepreferably for 5 seconds or longer but 5 minute or shorter, andparticularly preferably for 20 seconds or longer but 3 minutes orshorter. After the completion of the alkali saponification reaction, itis preferable to wash with water; or wash with an acid and then washwith water, the surface applied the saponifying solution.

The surface energy of the solid obtained by these methods can bemeasured by the contact angle method, the wet heating method, or theadsorption method, as described in “The basic theory and application ofwetting”, published by Realize Co., Ltd, Dec. 10, 1989. In the case ofthe cellulose acetate film of the present invention, the contact anglemethod is preferred. In that method, specifically, two solutions havingknown surface energies are dropped onto the cellulose acetate film.Then, the contact angle of each drop can be measured, and the surfaceenergy of the film can be determined by calculation from the measuredcontact angles. The contact angle is defined to be an angle which isformed by a tangent line and the film surface, the tangent line being aline tangent to the curve of the droplet, which line is drawn at thepoint where the droplet surface intersects the film surface, and thecontact angle being the angle at the droplet side.

It is possible to obtain a cellulose acetate film whose surface energyis 55 to 75 mN/m, by carrying out the above surface treatment of thecellulose acetate film. By using this cellulose acetate film as atransparent protective film of a polarizing plate, the adhesion of apolarizing film to the cellulose acetate film can be improved. Also,when the cellulose acetate film of the present invention is used in anOCB mode liquid crystal display device, the optical compensation sheetof the present invention may be provided with an stretched film formedon the cellulose acetate film and with an optically anisotropic layercontaining a disk-like compound or a rod-like liquid crystal compound onthe stretched film. The optically anisotropic layer is formed byorientating the disk-like compound (or the rod-like liquid crystalcompound) on the orientated film, to fix the orientation state. When theoptically anisotropic layer is formed on the cellulose acetate film inthis manner, it is conventionally necessary to form a gelatin undercoatlayer between the cellulose acetate film and the orientated film, tosecure the adhesion between the both. Contrary to the above, it isunnecessary to form such a gelatin undercoat layer, by using thecellulose acetate film of the present invention, which has a surfaceenergy of 55 to 75 mN/m.

(Polarizing Plate)

The polarizing plate comprises a polarizing film (a polarizer) and twotransparent protective films disposed on the both sides of thepolarizing film. The optical compensation sheet constituted by using theaforementioned cellulose acylate film can be used as at least one of theprotective films. A usual cellulose acetate film may be used as theother protective film.

Examples of polarizing films include iodine-based polarizing films, anddye- or polyene-based polarizing films using dichromatic dyes.Iodine-based polarizing films and dye-based polarizing films aregenerally produced, using polyvinyl alcohol-based films.

The slow axis of the optical compensation sheet comprising the celluloseacylate film is preferably placed substantially parallel to thetransmission axis of the polarizing film. Herein, the term “the slowaxis of the optical compensation sheet comprising a cellulose acylatefilm and the transmission axis of the polarizing film adjacent to saidcellulose acylate film are arranged in substantially parallel to eachother” means that an angle formed by the slow axis and transmission axisis generally within ±^(˜)2°, preferably within ±1°, to the axisdirection.

(Antireflection Layer)

An antireflection layer is preferably provided on a transparentprotective film that is placed on one side of the polarizing plateopposite to a liquid crystal cell. Particularly in the presentinvention, the antireflection layer is preferably a laminate of at leasta light scattering layer and a low-refractive-index layer provided inthis order on the transparent protective film, or a laminate of amiddle-refractive-index layer, a high-refractive-index layer and alow-refractive-index layer provided in this order on the transparentprotective film.

(Liquid Crystal Display Device)

The polarizing plate using the optical compensation sheet of the presentinvention can be used advantageously in a liquid crystal display device.The polarizing plate of the present invention may be used in liquidcrystal cells driven in various displaying modes. As for the displaymodes, proposed are various modes, for example, TN (Twisted Nematic),IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC(Anti-ferroelectric Liquid Crystal), OCB (Optically Compensatory Bend),STN (Supper Twisted Nematic), VA (Vertically Aligned), and HAN (HybridAligned Nematic). Among these, the present invention may be preferablyapplied to OCB-mode or VA-mode.

The present invention will be described in more detail based on thefollowing examples, but the invention is not intended to be limited tothese.

EXAMPLES Example 1 Preparation of Cellulose Acylate Film

The components in the following composition ratio were poured into amixing tank, and the resultant was stirred under heating, to dissolvethe components each other, thereby to prepare a cellulose acetatesolution.

(Composition of the cellulose acetate solution) Cellulose acetate(acetylation degree: 60.9%) 100 mass parts Triphenyl phosphate(plasticizer) 7.8 mass parts Biphenyldiphenyl phosphate (plasticizer)3.9 mass parts Methylene chloride (first solvent) 318 mass partsMethanol (second solvent) 47 mass parts Silica (particle diameter: 0.2μm) 0.1 mass parts

Another mixing tank was charged with any of retardation controllingagents A and B, as shown in Table 2 below, 87 mass parts of methylenechloride, and 13 mass parts of methanol, and the resultant mixture wasstirred under heating, to prepare retardation controlling agentsolutions, respectively.

Any one of the retardation controlling agent solutions was admixed withthe cellulose acetate solution, and the resultant mixture was thoroughlystirred, to prepare a dope. The amounts of the retardation controllingagents A and B to be added, to 100 mass parts of the cellulose acetate,are shown in Table 2. Further, Re/Rth ratios of the retardationcontrolling agents measured by the above-described method, are shown inTable 1.

The resulting dope was cast using a band casting machine, and theresulting film with a residual solvent content of 32% by mass at thestretching start time was laterally stretched at a stretch ratio of 26%with a tenter, under conditions of 130° C., followed by drying at 130°C. for 20 minutes, to give a cellulose acetate film (92 μm inthickness). With respect to the thus-prepared cellulose acetate film, Reretardation value and Rth retardation value at wavelength 590 nm weremeasured, using KOBRA 21 ADH (trade name, manufactured by Oji ScientificInstruments). The results are shown in Table 2.

TABLE 1 Re/Rth ratio of retardation-controlling agentRetardation-controlling agent Re (nm) Rth (nm) Re/Rth Compound (I-421)20 114 0.18 Compound (II-21) 34 145 0.23 Compound (III-23) 28 72 0.39Compound (IV-1) 25 138 0.18 Compound (IV-4) 26 70 0.37

TABLE 2 Properties of the prepared films Retardation-controlling agentAmount of Amount of Example Controlling addition of A Controllingaddition of B Re Rth No. agent A (mass %) agent B (mass %) (nm) (nm)Re/Rth Example 1 Compound 2 Compound 2 60 128 0.47 (I-421) (III-23)Example 2 Compound 5 Compound 2 75 190 0.39 (I-421) (III-23) Example 3Compound 2 Compound 2 72 170 0.42 (II-21) (III-23) Example 4 Compound 3Compound 2 90 180 0.5 (II-21) (III-23) Example 5 Compound 2 Compound 266 182 0.36 (IV-1) (III-23) Example 6 Compound 2 Compound 2 54 132 0.41(I-421) (IV-4) Comparative Compound 2 None 0 24 115 0.21 example 1(I-421) Comparative Compound 6 None 0 38 190 0.02 example 2 (I-421)Comparative Compound 2 None 0 43 152 0.28 example 3 (II-21) ComparativeCompound 3 None 0 56 201 0.28 example 4 (II-21) Comparative Compound 2None 0 34 75 0.44 example 5 (III-23) Comparative Compound 2 None 0 26142 0.18 example 6 (IV-1) Comparative Compound 2 None 0 26 73 0.36example 7 (IV-4)

As can be understood from Table 2, when the compound represented byformula (I) or (II) was used singly, Re was possible to be made large,but Rth was also made large at the same time. Further, when the compoundrepresented by formula (III) was used singly, Rth did not become large,but Re could not be made large, and the range of Re and Rth could not befreely set. Contrary to the above, according to the present invention,the use of a combination of the compounds different in Re/Rth ratioseach other allowed to give the optical compensation films with desiredRe values (60 to 90 nm) and desired Rth values (128 to 190 nm).

Further, the compounds represented by formula (IV) is classified intotwo types: the first type includes (IV-1), which behaves in a mannersimilar to the compound represented by formula (I) or (II); and thesecond type includes (IV-4), which behaves in a manner similar to thecompound represented by formula (III). Similar to the above, althoughsingle use of only one type of the above two gave Re and Rth adjustedinsufficiently, a combined use of these two types of the compoundsrepresented by formula (IV) gave an optical compensation film, in whichRe and Rth were adjusted in their respective preferable ranges.

Further, these films were processed into polarizing plates, which wereused for optical compensation. As a result, optical compensation couldbe easily performed on a wide variety types of liquid crystal displaydevices.

INDUSTRIAL APPLICABILITY

The optical compensation sheet of the present invention is preferable tobe applied in a wide variety types of liquid crystal display devices ina simple structure, without increasing the number of components in thepolarizing plate utilized in said display devices.

Having described our invention as related to the present embodiments, itis our intention that the invention not be limited by any of the detailsof the description, unless otherwise specified, but rather be construedbroadly within its spirit and scope as set out in the accompanyingclaims.

1. An optical compensation sheet, comprising a cellulose acylate filmthat contains 1 to 20 parts by mass of a retardation controlling agent,to 100 parts by mass of a cellulose acylate, wherein the retardationcontrolling agent comprises at least two compounds different in Re/Rthratios from each other; wherein one of the at least two compoundscontained in the retardation controlling agent is selected from thegroup consisting of formulas (I), (II) and (IV) and exhibits a Re/Rthratio of less than 0.35, and the other is selected from the groupconsisting of formulas (III) and (IV) and exhibits a Re/Rth ratio of notless than 0.35;

wherein in Formula (I), X¹ represents a single bond, —NR⁴—, —O—, or —S—;X² represents a single bond, —NR⁵—, —O—, or —S—; X³ represents a singlebond, —NR⁶—, —O—, or —S—; R¹, R² and R³ each independently represent analkyl group, an alkenyl group, an aryl group, or a heterocyclic group;and R⁴, R⁵ and R⁶ each independently represent a hydrogen atom, an alkylgroup, an alkenyl group, an aryl group, or a heterocyclic group;Ar¹-L¹

Ar²-L²

_(n)Ar³  Formula (II) wherein in Formula (II), Ar¹, Ar², and Ar³ eachindependently represent an aryl group or an aromatic heterocyclic group;L¹ and L² each independently represent a single bond or a divalentlinking group; n represents an integer of 3 or more; and a plurality ofthe Ar² moieties may be the same or different, and a plurality of the L²moieties may be the same or different;Ar¹¹-L¹²-X-L¹³-Ar¹²  Formula (III) wherein in Formula (III), Ar¹¹ andAr¹² each independently represent an aromatic group; L¹² and L¹³ eachindependently represent a divalent linking group selected from the groupconsisting of an alkylene group, —O—, —CO—, and a combination thereof;and X represents 1,4-cyclohexylene, vinylene, or ethynylene;

wherein in Formula (IV), R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ each independentlyrepresent a hydrogen atom or a substituent.
 2. The optical compensationsheet as claimed in claim 1, wherein the optical compensation sheetcomprises a cellulose acylate film stretched at a stretch ratio of 3 to100%.
 3. The optical compensation sheet as claimed in claim 1, whereinthe content of the two compounds contained in the retardationcontrolling agent is 1 to 20 parts by mass in sum, to 100 parts by massof the cellulose acylate.
 4. The optical compensation sheet as claimedin claim 1, wherein the compound exhibiting a Re/Rth ratio of less than0.35 is represented by formula (I):

wherein X¹ represents a single bond, —NR⁴—, —O—, or —S—; X² represents asingle bond, —NR⁵—, —O—, or —S—; X³ represents a single bond, —NR⁶—,—O—, or —S—; R¹, R² and R³ each independently represent an alkyl group,an alkenyl group, an aryl group, or a heterocyclic group; and R⁴, R⁵ andR⁶ each independently represent a hydrogen atom, an alkyl group, analkenyl group, an aryl group, or a heterocyclic group.
 5. The opticalcompensation sheet as claimed in claim 1, wherein the compoundexhibiting a Re/Rth ratio of less than 0.35 is represented by formula(II):Ar¹-L¹

Ar²-L²

_(n)Ar³  Formula (II) wherein Ar¹, Ar², and Ar³ each independentlyrepresent an aryl group or an aromatic heterocyclic group; L¹ and L²each independently represent a single bond or a divalent linking group;n represents an integer of 3 or more; and a plurality of the Ar²moieties may be the same or different, and a plurality of the L²moieties may be the same or different.
 6. The optical compensation sheetas claimed in claim 1, wherein the compound exhibiting a Re/Rth ratio ofnot less than 0.35 is represented by formula (III):Ar¹¹-L¹²-X-L¹³-Ar¹²  Formula (III) wherein Ar¹¹ and Ar¹² eachindependently represent an aromatic group; L¹² and L¹³ eachindependently represent a divalent linking group selected from the groupconsisting of an alkylene group, —O—, —CO—, and a combination thereof;and X represents 1,4-cyclohexylene, vinylene, or ethynylene.
 7. Theoptical compensation sheet as claimed in claim 1, wherein theretardation controlling agent is a compound represented by formula (IV):

wherein R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ each independently represent ahydrogen atom or a substituent.
 8. A liquid crystal display device,comprising a liquid crystal cell, and two polarizing plates disposed onboth sides of the liquid crystal cell, said polarizing plate comprisinga polarizing film and two transparent protective films disposed on bothsides of the polarizing film, wherein the optical compensation sheet asclaimed in claim 1 is disposed between the liquid crystal cell and atleast one polarizing film, and wherein a slow axis of the celluloseacylate film and a transmission axis of the polarizing film adjacent tothe cellulose acylate film are arranged in substantially parallel toeach other.
 9. The optical compensation sheet as claimed in claim 1,wherein the difference between the Re/Rth ratios of the two compounds is0.05 or more.
 10. The optical compensation sheet as claimed in claim 1,wherein the compound that exhibits a Re/Rth ratio of less than 0.35 is acompound that exhibits a Re/Rth ratio of 0.18 or more but less than0.35, and the compound that exhibits a Re/Rth ratio of not less than0.35 is a compound that exhibits a Re/Rth ratio of 0.35 or more but 0.39or less.
 11. The optical compensation sheet as claimed in claim 1,wherein the cellulose acylate film has a Re retardation value of 60 to120 nm and an Rth retardation value of 100 to 250 nm.